PressureSwingAdsorption TechnicalAnalysis

PG&E GAS R&D AND INNOVATION
Pressure Swing
Adsorption Technical
Analysis
7/2/2018
PG&E GAS R&D AND INNOVATION TECHNICAL ANALYSIS:
PRESSURE SWING ADSORPTION
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PAGE 2 OF 12
“PG&E” refers to Pacific Gas and Electric Company, a subsidiary of PG&E Corporation. © 2019 Pacific Gas and Electric Company. All rights reserved.
Table of Contents
What is Pressure Swing Adsorption (PSA) ..................................................................................................................4
Drawbacks of PSA .......................................................................................................................................................6
Economic Benefits ......................................................................................................................................................7
Common Adsorption Materials ..................................................................................................................................7
Companies that commercialize PSA technology ..................................................................................................... 12
References ............................................................................................................................................................... 12
Table of Figures
Figure 1 Graph showing the relationship between adsorbed CO2 and pressure .......................................................4
Figure 2 Illustration of the Skarstrom Cycle ...............................................................................................................6
Figure 3 Picture of zeolites .........................................................................................................................................8
Figure 4 Picture of activated carbon ..........................................................................................................................8
Figure 5 Picture of silica gel and aluminum oxide ......................................................................................................9
Figure 6 Picture of molecular sieves...........................................................................................................................9
Figure 7 PSA process diagram ................................................................................................................................. 10
Figure 8 List of compounds and their adsorption force strength ........................................................................... 10
Table of Tables
Table 1 Comparison of different biogas upgrading technologies ........................................................................... 11
PAGE 3 OF 12
What is Pressure Swing Adsorption (PSA)

A technology used to separate and purify components of a gas mixture under pressure according to each
component’s molecular characteristics and affinity for a specific adsorbent material. Specific adsorptive
materials preferentially adsorb a target gas at pressure. The pressure is then swung low to desorb the adsorbed
material, leaving a purer gas.
• Under high pressure, gases tend to be attracted to solid surfaces, a phenomenon known as adsorption. Gas
components are separated because different gases are attracted to different solid surfaces at different
intensities.
• Since heating and cooling is not part of the process, the cycle time can be in the range of minutes. The
adsorbent material has a very long lifetime compared to other upgrading technologies.
• Flow rates range from small scale at 10 m3/hr to larger scale at 10,000 m3/hr. (Grande, 2011)
• An attractive gas upgrading technology due to compactness of the equipment, low energy requirements,
low capital costs, and simple operation (Augelletti, 2017).
Figure 1 Graph showing the relationship between adsorbed CO2 and pressure (Bauer, 2012)
A methane recovery greater than 99% can be obtained with an energy consumption of 1250 kJ per kg of
biomethane. Mixing blowdown gas with raw biogas, methane recovery can be increased by up to 5%.
(Petersson, 2009)
PAGE 4 OF 12
There is a variant to PSA called rapid cycle PSA which will operate at a speed of 5-20 times conventional PSA.
Rapid cycle PSA is carried out by using multi-port selector rotary valves and a many smaller adsorption
chambers. These systems are typically smaller in size, have lower capital costs, lower pressure drops, and higher
throughputs. The downside of rapid cycle PSA is the methane recovery rate. One of the largest suppliers of
rapid cycle PSA systems is Xebec Inc. which can maintain a capacity of 150 to 5,000 Nm3/hr of biogas. (Xebec
Adsorption, 2017)
Four Steps (Skarstrom Cycle): (Bauer, 2012)
• Pressurization: The raw biogas is pressurized in the vessel to 4-10 bar.

• Feed/Adsorption: The raw biogas is fed into the tank and the targeted compounds start to become
attracted to the solid adsorption surface as the methane flows through the column. When the adsorption
bed is saturated, the feed is closed and the blowdown phase is initiated.
• Blowdown: Once the adsorption bed is saturated, and the upgraded methane was moved through, the feed
is close. The pressure inside the vessel is lowered considerable to desorb the carbon dioxide from adsorbent
and the carbon dioxide rich gas is pumped out of the vessel.
• Purge: At the lowest column pressure, the purge is initiated.
PAGE 5 OF 12
Since this cycle contains four phases, it is common for PSA units to have four columns. The PSA cycle usually
lasts between 2-10 minutes long.
Figure 2 Illustration of the Skarstrom Cycle (Bauer, 2012)
The vent gas can be torched (if the methane content is high enough), or it can be catalytically oxidized in a
special vessel to prevent methane leakage. Another option is for the vent gas to be combined with the raw
biogas to be combusted to produce heat to be used locally.
Typically, multiple vessels are used in parallel to improve energy efficiency and to smooth gas production rate.
Drawbacks of PSA
Compared to other upgrading technologies, there is a relatively high amount of methane that is captured in the
off gas rather than the captured gas. This off gas with require further upgrading if you are looking for a pure CO2
stream. Methane recovery rates can range from 60 to 80%. The balance of methane leaves the system in the
tail gas with the desorbed CO2. This tail gas can be upgraded further by recycling back into the PSA system.
Moisture will need to be removed prior to biogas entering PSA system because water can block the adsorbent’s
micropores, reducing system performance. Could require high levels of electricity to achieve high pressure
levels used in the process. (Grande, 2011)
PAGE 6 OF 12
Economic Benefits
• Low energy consumption, does not consume water or create contaminated waste water. Does not require
any heat.
• High purity levels

• Relatively low investment and maintenance costs
Common Adsorption Materials

Adsorbents are usually very porous materials because of their large surface areas. Adsorbent material will need
to be replaced once it is filled or when it has reached its regenerated limit. In general, adsorbent material
require minimal maintenance and are inexpensive. The setup is simple: adsorbent material is place in a drum
with a gas inlet and an outlet.
The two main criteria for an attractive adsorption material:

• Have a high selectivity to CO2. We want the material to have a higher affinity towards CO2 than methane.
• Be of a material that has pores that CO2 can penetrate their structure, while larger CH4 molecules have size
limitations to diffuse through them. These materials are called kinetic adsorbents because their selectivity
mechanism is through diffusion constraints.
Zeolites:
• One of the most common adsorbents used in PSA
• Naturally occurring or synthetic silicates with uniform pore size and dimensions.
• They work best with polar compounds such as H2S, SO2, NH3, carbonyl sulfide, mercaptans
PAGE 7 OF 12
Figure 3 Picture of zeolites
https://www.igb.fraunhofer.de/en/research/competences/physical-process-technology/heat-and-sorption-
systems/sorptive-heat-storage/projects/hipel.html
Activated Carbon:
• Most commonly used adsorbent due to low cost, widespread availability, high surface area, and adsorptive
affinity to hydrogen sulfide, carbon dioxide, moisture, VOCs, halides, and siloxanes.
• Surface area of 500 – 2500 m3/g (usually 1500)
• Capacity of 20-25% loaded by weight of H2S
Figure 4 Picture of activated carbon
https://www.hmicronpowder.com/industries/chemical/activated-carbon
PAGE 8 OF 12
Silica Gel and Aluminum Oxide:

• These can remove siloxanes and moisture by trapping them within their crystalline structure.
• Regenerate by exposing to high temperature and high pressure.
Figure 5 Picture of silica gel and aluminum oxide
http://www.preservationcare.com/shop/silica-gel
Molecular Sieves:
• Carbon molecular sieves are kinetic adsorbents that have micropores allowing contaminant molecules to
penetrate faster than methane.
• Note that activated carbon and zeolites can also act as molecular sieves.
Figure 6 Picture of molecular sieves
http://www.kuraray-c.co.jp/en/products/device.html
PAGE 9 OF 12
A “dry” method, meaning there are no solvents or washing liquid. Based on columns filling with adsorption
materials which operate in a rotating/non-continuous mode.
Figure 7 PSA process diagram (Kaffka, 2014)
Figure 8 List of compounds and their adsorption force strength (Keller, 2016)
PAGE 10 OF 12
Table 1 Comparison of different biogas upgrading technologies (Langerak, 2018)
Pressurized Pressure
Membrane Cryogenic
Water Catalytic Swing
Separation Liquefaction Unit
Scrubbing Absorption Adsorption
(MS) (CL)
(PSW) (PSA)
Produced Gas
98 99 97-99 99 99.5 % CH4
Quality
Methane Slip 1 01 – 0.2 1 -3 0.3 – 0.5 0.5 %
Electrical Use 0.23 – 0.25 0.15 – 0.18 0.25 0.21 – 0.24 0.35 kWh/feed
kW/Nm3
Reliability/Up Time 96 94 94 98 94
product
Turn Down Ratio 50 – 100 50 – 100 85 – 100 0 – 100 75 – 100 %
CAPEX Medium Medium Medium Low High %
Operations Cost Low Medium Medium Low High
Foot Print Large Large Medium Small Large
Maintenance
Medium Medium+ Medium+ Low High
Needed
Ease of Operation Medium Medium+ Medium Easy Complex
AC =
Consumables/Waste
AC*3/Water AC*3/amines AC*3/adsorbents AC*3/none AC*3/None Activated
Streams
Carbon
PAGE 11 OF 12
Companies that commercialize PSA technology

• Carbotech (www.carbotech.de)
• Acrona (www.acrona-systems.com)
• Cirmac (www.cirmac.com)
• Gasrec (www.gasrec.co.uk)
• Xebec Inc. (www.xebecinc.com)
• Guild Associates (www.moleculargate.com)
References
Augelletti, R. (2017, January 1). Pressure Swing Adsorption for biogas upgrading. A new process configuration for the separation of
biomehtane and carbon dioxide. Retrieved from ScienceDirect:
https://www.sciencedirect.com/science/article/pii/S0959652616316110
Bauer, F. (2012). Biogas Upgrading - Review of Commerical Technologies. Retrieved from SGC:
http://vav.griffel.net/filer/C_SGC2013-270.pdf
Grande, C. A. (2011, August). Biogas Upgrading by Pressure Swing Adsorption. Retrieved from Intech:
https://cdn.intechopen.com/pdfs-wm/17476.pdf
Kaffka, S. R. (2014, October). Draft: Comparative Assessment of Technology Options for Biogas Clean-Up. Retrieved from California
Biomass Collaborative: https://biomass.ucdavis.edu/wp-content/uploads/Biogas-Cleanup-
Report_FinalDraftv3_12Nov2014-2.pdf
Keller, T. (2016, January 1). PSA Technology: Beyond Hydrogen Purification. Retrieved from Chemical Engineering:
https://www.chemengonline.com/psa-technology-beyond-hydrogen-purification/?printmode=1
Langerak, J. (2018, May 19). Biogas to Biomethane Conversion Technologies. Retrieved from BioEnergy Consult:
https://www.bioenergyconsult.com/tag/pressure-swing-adsorption/
Petersson, A. (2009, October). Biogas Upgrading Technologies - Developments and Innovations. Retrieved from IEA Bioenergy:
https://www.iea-biogas.net/files/daten-redaktion/download/publi-task37/upgrading_rz_low_final.pdf
Xebec Adsorption. (2017, March 16). Xebec Announces Biogas Upgrading Breakthrough. Retrieved from Biomass Magazine:
http://biomassmagazine.com/articles/14257/xebec-announces-biogas-upgrading-breakthrough
PAGE 12 OF 12

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PG&E GAS R&D AND INNOVATION

What is Pressure Swing Adsorption (PSA)

Four Steps (Skarstrom Cycle): (Bauer, 2012)

• Pressurization: The raw biogas is pressurized in the vessel to 4-10 bar.

Figure 2 Illustration of the Skarstrom Cycle (Bauer, 2012)

• High purity levels

Common Adsorption Materials

The two main criteria for an attractive adsorption material:

Figure 3 Picture of zeolites

• Surface area of 500 – 2500 m3/g (usually 1500)

• Capacity of 20-25% loaded by weight of H2S

Figure 4 Picture of activated carbon

Silica Gel and Aluminum Oxide:

• Regenerate by exposing to high temperature and high pressure.

Figure 5 Picture of silica gel and aluminum oxide

Figure 6 Picture of molecular sieves

Figure 7 PSA process diagram (Kaffka, 2014)

Table 1 Comparison of different biogas upgrading technologies (Langerak, 2018)

Methane Slip 1 01 – 0.2 1 -3 0.3 – 0.5 0.5 %

Turn Down Ratio 50 – 100 50 – 100 85 – 100 0 – 100 75 – 100 %

CAPEX Medium Medium Medium Low High %

Operations Cost Low Medium Medium Low High

Foot Print Large Large Medium Small Large

Ease of Operation Medium Medium+ Medium Easy Complex

Companies that commercialize PSA technology

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